VIETNAM NATIONAL UNIVERSITY

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

FACULTY OF CHEMICAL ENGINEERING DEPARTMENT
OF PETROLEUM PROCESSING TECHNOLOGY

SPECIALIZED PROJECT IN CHEMICAL ENGINEERING REPORT

SYNTHESIS OF ZEOLITE X USING HIGH FREQUENCY WAVES

Instructor: Dr. Tran Hai Ung

Host of department: TS. Pham Ho My Phuong
Student name: Nguyen Phan Vu Hoai
Student’s ID: 2153356

Ho Chi Minh City, 2024

1
HCMC University of Technology SOCIAL REPUBLIC OF VIETNAM
Faculty: Chemical Engineering Independence – Freedom – Happiness
Department of Petroleum processing technology

CHEMICAL ENGINEERING SPECIALIZED

Student name: Nguyễn Phan Vũ Hoài Student number: 2153356
Department: Petroleum processing technology Class: CC21HDK
1. Research Topic
Sythesis of Zeolite X using high frequency waves
2. Report content:
Overview of Zeolite
Synthesis Zeolite X using High frequency waves
3. Instructor: Dr. TRAN HAI UNG
4. Project – starting date:
5. Complete date:
HEAD OF DEPARTMENT INSTRUCTOR

Dr. PHAM HO MY PHUONG Assoc. Prof. TRAN HAI UNG

2
LETTER OF THANKS

3
 Contents
CHAPTER 1: OVERVIEW OF ZEOLITE.........................................................................................3
1.1 Origin.............................................................................................................................................3
1.2 Definition of Zeolite......................................................................................................................3
1.3. Application of Zeolite X..............................................................................................................3
1.4. Classification................................................................................................................................5
1.4.1 Classification by origin...........................................................................................................5
1.4.2. Classification by.....................................................................................................................5
1.5. Structure.......................................................................................................................................5
1.6. Synthesis of Zeolite X..................................................................................................................5
CHAPTER 2: SYNTHESIS ZEOLITE X USING HIGH FREQUENCY WAVES..........................7
2.1. Overview of High Frequency waves...........................................................................................7

1
OPENING

2
 CHAPTER 1: OVERVIEW OF ZEOLITE
1.1 Origin
Zeolites are a group of hydrated aluminosilicate minerals that have a crystalline
structure and are known for their ability to absorb water and other molecules. The term
"zeolite" comes from the Greek words "zeo," meaning "to boil," and "lite," meaning "stone,"
which reflects the way these minerals release water when heated.
The first zeolite to be discovered was natural zeolite, which was identified in the 18th
century. The mineral was first described by the Swedish mineralogist Axel Fredrik Cronstedt
in 1756. Since then, over 40 different natural zeolites have been discovered, with many others
being synthesized for various applications.
Zeolites occur naturally in volcanic ash layers and are formed through the process of
mineral hydration and crystallization. They can also be synthesized in laboratories for use in a
wide range of applications, including water purification, gas separation, catalysis, and as soil
amendments in agriculture.
1.2 Definition of Zeolite
Zeolites are aluminosilicates that have a very uniform pore size, allowing for the selective
separation of components based on their specific sizes. The chemical formula of zeolites is as
follows:

(M*)x [(AlO2)x (SiO2)y]. zH2O

Where:

 M: is the cation that balances the negative charge

 Z: is the number of H₂O molecules bonded in the zeolite

 [ ]: is the structural unit of the zeolite framework

 y/x: is the ratio of Si/Al, referred to as the module of zeolite. This ratio varies
depending on the type of zeolite.

 If y/x≥1y/x≥1 (according to the Lowenstein rule, it indicates that there is a connection

between Si-O-Al and Si-O-Si; Al-O-Al does not exist)

Zeolites are crystalline aluminosilicates with a three-dimensional spatial structure that

has a uniform and very orderly system of pores. The internal space consists of small cavities
connected by stable tunnels. Thanks to this system of pores and tunnels, zeolites can adsorb
molecules smaller than their pore size and expel those larger than their size. Because of this
capability, zeolites are considered a type of "molecular sieve." Zeolites are formed when

3
aluminum replaces some silicon atoms in the crystalline structure of silicon oxide. Since
aluminum atoms (trivalent) replace silicon atoms (quadrivalent), the zeolite crystal lattice has
a negative charge. The amount of negative charge is equal to the number of aluminum atoms
in the lattice. To ensure electrical neutrality, zeolites need cations to compensate for the excess
negative charge. In nature or in the initial synthetic form, these cations are often alkali metal
cations (Na+, K+) or alkaline earth metal cations (Mg2+, Ca2+). These cations are located
outside the zeolite crystal lattice and can easily participate in ion exchange processes with
ammonium cations or other multivalent cations. It is these properties that allow zeolites to be
modified and provide them with a wide range of attractive properties and applications in
adsorption and catalysis.
Zeolite X

1.3. Application of Zeolite X

Zeolite X, a type of synthetic zeolite with a unique crystalline structure and high
surface area, has a variety of applications across different fields. Here are some of its main
applications:

Catalysis: Zeolite X is widely used as a catalyst in petrochemical processes, including

the fluid catalytic cracking (FCC) process. It helps in breaking down larger hydrocarbon
molecules into gasoline and other fuels. This process is initiated by the separation of
unrefined petroleum into different products, from ones withsmall (methane) to ones with big
(tar) molecules. Zeolite X plays a crucial role in catalytic processes due to its porous structure
and high surface area. Otherwise, catalytic is utilized as a solid-acid catalyst in various
reactions, especially in hydrocarbon processing and organic synthesis. Its ability to facilitate
reactions such as alkylation, isomerization, and cracking is well-documented 1. Another
application is enhanced Mass Transfer which the hierarchical structure of zeolite X improves
mass transfer capabilities, thus increasing its effectiveness in catalytic applications compared
to traditional zeolites2. Some explames of the product are showed in the diagram below:

1
Chen, S., Seo, D. K., & Chang, S. (2017). Imaging Hydrated Nanostructured Zeolite X using Single-Electron-
Detection Camera. Microscopy and Microanalysis.
https://www.semanticscholar.org/paper/73f14977308ab6cb3edd731f3cc10ea959b6bc1d
2
Liu, B., Fei, C., Liming, Z., Jinghui, G., Xi, H., & Qian, Y. (2013). Synthesis and structural properties of
hierarchically structured aluminosilicates with zeolite Y (FAU) frameworks. RSC Advances.
https://www.semanticscholar.org/paper/596a551fc3b6e1a296470aa303366f351761dc23

4
 Figure 1 Catalytic Craking FCC Process3
Ion Exchange and Water Treatment: Given natural zeolites structure we can deduct
that the negative charge on the surface is due to the fact that silicon and aluminium, which are
present in the basic structure, have four and three electrons respectively, which are available
to form bonds with other atoms. In the small pores present in the structure of zeolites, there
are some exchangeable ions and it is also the place where the exchange of ions takes place.
Due to its ion-exchanging capabilities, Zeolite X is used in water purification processes to
remove heavy metals, ammonium ions, and other contaminants. It can also soften water by
exchanging calcium and magnesium ions for sodium ions. In heavy metal removal, it
effectively removes cations and heavy metals from water, enhancing the quality of treated
water. Its unique structure allows it to selectively uptake ions such as lead and cadmium,
making it suitable for environmental remediation4. Additionally, in radionuclide capture, the
zeolite can ion-exchange cesium ions, thus finding application in treating nuclear waste and
contaminated water, exemplified by its use in managing radioactive waste streams.

For water treatment, Zeolite X is an advanced material used in water treatment

processes, offering enhanced performance compared to traditional filtering agents like sand
and carbon. Its negatively charged structure allows for effective ion exchange, enabling it to
adsorb cations such as heavy metals and ammonia from water. This process purifies and filters
water by retaining harmful pollutants, with its porous architecture facilitating the retention of
particles while selectively allowing the passage of cleaner water. Additionally, its high
3
Alfa Laval. (n.d). Catalytic cracking [Image]. https://www.alfalaval.lat/industrias/energia-y-utilities/refineria-
de-crudo-petrolifero/catalytic-cracking/
4
Marchuk, V., et al. ..Li/Catalysis Catalysis Science & Technology. Jan. 2023,
https://www.semanticscholar.org/paper/f0bc0970d1a3ce5ab2d26c371fab94e9462b0dad.

5
adsorption capacity and longer service life make it ideal for uses such as swimming pool
filtration, where it requires fewer wash cycles and conserves water compared to sand filters.
Animal Feed Additive: Zeolite X is also used in animal nutrition as a feed additive to
improve gut health and nutrient absorption, as well as to mitigate mycotoxin effects. Its
porous structure aids in promoting beneficial gut bacteria while adsorbing harmful
mycotoxins, thus mitigating their toxic effects on livestock. Additionally, it facilitates the slow
release of essential minerals, ensuring animals derive maximum benefit from their feed. As a
result, Zeolite X contributes to better growth rates and overall animal performance, making it
a valuable component in modern animal husbandry practices.

Construction Materials: It can be incorporated into construction materials like

concrete to improve durability and reduce permeability. Its lightweight properties contribute
to lower overall weight in construction. In China, for example, natural zeolites are used to
partially replace Portland cement. This is due to their ability to retain water within their
structure, which is released evenly as the concrete sets. Additionally, the resulting concrete
made from the combination of cement and zeolite is not only highly durable but also
significantly lighter than conventional concrete. As a result, zeolite X is used as a
lightweight aggregates since it can be used in the production of lightweight aggregates for
concrete, which improves the thermal insulation properties of building materials 5. On the
other hand, it is also used in ustainable building Materials, which its presence in cement
formulations enhances mechanical strength and durability while also offering an avenue for
recycling industrial waste materials into construction product.

Pharmaceutical Applications: In the pharmaceutical industry, Zeolite X is researched

for drug delivery systems and as a carrier for certain medications due to its porous structure
and ability to control the release of drugs. In Drug delivery, tt can serve as a drug delivery
system, wherein drugs are encapsulated within the zeolite structure, ensuring controlled
release6. While in Antimicrobial Properties, zeolite X has been studied for its potential
antimicrobial properties, potentially opening up avenues for developing hygiene-promoting
materials

5
Liu, Baoyu, et al. “Synthesis and Structural Properties of Hierarchically Structured
Aluminosilicates with Zeolite Y (FAU) Frameworks.” RSC Advances, Aug. 2013,
https://www.semanticscholar.org/paper/596a551fc3b6e1a296470aa303366f351761dc23.
6
Tirado, Juan I., et al. “Crystal Structure of Zeolite A Solved by Precession Electron
Diffraction Tomography.” Acta Crystallographica Section A Foundations and Advances,
Aug. 2021,
https://www.semanticscholar.org/paper/71723e042e044b3d943eb2d4edcd5896a3b0a079
.

6
 Waste Treatment: Zeolite X can be utilized in the treatment of wastewater and
industrial effluents, helping to adsorb and remove pollutants such as heavy metal,
contaminants,...

1.4. Classification
1.4.1. Structural Classification

 Framework Type: Zeolite X is classified under the framework type FAU, which is
characterized by a three-dimensional pore structure comprised of large supercages, allowing
for the accommodation of various cations and molecules.
 Pore Size: The pore openings of zeolite X generally range from 7.4 Å to 8.0 Å, which
facilitates the adsorption and exchange of various cationic species.
 Tetrahedral Framework: The structure consists of a framework built from tetrahedral
arrangements of SiO4 and AlO4 units, contributing to its ion-exchange properties and catalytic
activity.

1.4.2. Chemical Classification

 Aluminosilicate Composition: Zeolite X primarily consists of silicon dioxide (SiO2) and

aluminum oxide (Al2O3) in varying ratios, which influences its ion-exchange capacity and
adsorptive properties.
 Cation Exchange: The zeolite can be classified based on the cations present in its chemically
active sites. Common cations include sodium (Na+), potassium (K+), and calcium (Ca2+),
with sodium forms often being referred to as Na-Zeolite X.

1.4.3. Application-Based Classification

 Catalytic Applications: Zeolite X is utilized in catalytic cracking and various hydrocarbon

transformations due to its acid sites and pore structure, making it effective in the
petrochemical industry
 Environmental Applications: It serves as an effective ion-exchanger and adsorbent in water
treatment processes for removing heavy metals and organic dyes, such as methylene blue,
from wastewater.
 Construction Materials: As a pozzolanic material, zeolite X is being researched for its
potential use in eco-friendly concrete, enhancing mechanical properties and durability.

1.5. Structure
X-type zeolite has the faujasite (FAU) structure and its typical chemical composition
is: Na2O · Al2O3· 2.5SiO2· 6H2O. Zeolite X is usually synthesized in the sodium form with a
Si/Al ratio of 1–1.5, so it is strongly hydrophilic, and its pore size estimated from its crystal
structure is 0.74 nm. In Zeolite X, the SiO4 and AlO4 tetrahedra form the backbone of the

7
framework. Each tetrahedron is connected through shared oxygen atoms (bridging oxygens).
The basic building units are [SiO4] and [AlO4] tetrahedra. The aluminum content creates a
negative charge in the framework, balanced by exchangeable cations (usually sodium ions).

Cages: The framework forms large voids known as sodalite and supercages, characterized by:

Sodalite cavity: Approximately 1.2 nm in diameter.

Supercage: Approximately 1.3 nm in diameter with a unique 3-dimensional network.

Channels: Interconnected channels enable the transport of ions and molecules, contributing to
its catalytic properties.

1.6. Synthesis of Zeolite X

1.6.1. Hydrothermal method
The synthesis of zeolites can be shorted as three processes as follows:

 Gel formation
 Aging
 Crystallization

For gel formation this is the initial step where the precursors (sources of silica and alumina), along
with water and sufficient alkalinity (often sodium hydroxide or potassium hydroxide), are mixed to
create a homogeneous gel.To be specific the process can be expressed as: Firstly, the Precursor
Selection can be used from common silica sources include fumed silica, silica gel, and sodium silicate.
And Alumina sources can be alumina gel or aluminum hydroxide. Secondly, using Alkaline Solution
to alter the pH, promoting the formation of silicate and aluminate species that can polymerize.Thirdly
is the Mixing step, the precursors are mixed in precise molar ratios (Si/Al ratio) to produce a gel. With
the typical Si/Al ratio for zeolite X is around 2.0-2.5.And finally, it is the Homogenization where the
mixture is usually stirred to ensure thorough mixing and uniformity.

Next is the Aging process, Aging is the process where the gel is allowed to stand for a certain period to
promote the development of crystalline precursors before crystallization begins. And the Process are
showed below:

 Retention Time: The gel is left undisturbed at room temperature or slightly elevated
temperatures for a set time (hours to days), depending on the formulation and desired
characteristics.

 Chemical Changes: During aging, dissolved silicate and aluminate species can reorganize and
polymerize, leading to the formation of an intermediate phase that is more conducive to
zeolite crystallization.

 Viscosity Increase: The extent of aging can affect the viscosity of the gel, ultimately
influencing the size and morphology of the zeolite crystals formed later.

8
For the third process – Crystallization. This is the final step where the aged gel is subjected to heat
(usually in a hydrothermal environment) to induce the formation of zeolite crystals. When start
heating, the aged gel is typically transferred to an autoclave and heated at high temperatures (usually
between 80°C to 200°C) for a specified period (hours to days). Otherwise the Hydrothermal conditions
is important whent the environment in the autoclave maintains high pressure and controlled humidity,
which facilitates crystal growth. Additionaly, Nucleation and Growth are also considered, initially,
crystal nuclear form, which then grow into larger crystals. Furthermore, the conditions can be tweaked
(e.g., temperature, time, and seed crystals) to control the crystal size and purity. Finally is the cooling
and filtration part where the mixture is cooled after crystallization is complete, and the zeolite crystals
are separated by filtration, washed, and dried.

And here is a example of a simple diagram of synthesis Zeolite X Powder from Natural Low-Grade
Diatomite

Figure 2 Graphical abstract of producing Zeolite X7

Initially, diatomite and Al(OH)3 were mixed in a NaOH solution with vigorous magnetic stirring to
create a uniform dispersion. The quantities of diatomite and Al(OH)3 were adjusted to maintain a
molar ratio of 1.13 for [Si/Al], while the NaOH solution was prepared according to specific molar
ratios of [Na2O/SiO2] and [H2O/Na2O]. The resulting slurry was then aged for 0 to 120 minutes at
temperatures between 30°C and 60°C. After aging, the mixture was transferred into a Teflon-lined
stainless steel autoclave, which was then sealed. Crystallization occurred at temperatures ranging from
90°C to 120°C for a duration of 3 to 9 hours. Following crystallization, the autoclave was allowed to
cool naturally to room temperature. The samples were extracted from the reactor, filtered, and washed
7
Yao, G., Lei, J., Zhang, X., Sun, Z., & Zheng, S. (2018). One-Step Hydrothermal Synthesis of Zeolite X
Powder from Natural Low-Grade Diatomite. Porous Materials for Environmental Applications, 11(6), 906.
https://doi.org/10.3390/ma11060906

9
with deionized water until the pH of the filtrate reached 6 to 7. Lastly, the wet solids were dried
overnight at 105°C prior to further measurement and characterization.

1.6.2. Synthesis zeolite X by microwave assisted hydrothermal method

The nanometer-sized faujasite-X zeolite is synthesized using microwave heating techniques. In

heating methods, a 250 mL polypropylene bottle was initially washed with double de-ionized water
and secondly, aluminosilicate gel was made by mixing freshly prepared aluminate and silicate
solutions together in the molar ratio of 5.5 Na 2O:1.0 Al2O3:4.0 SiO2:190 H2O. Next, preparing an
aluminosilicate gel containing 5.34 g of NaOH, 2.42 g of NaAlO2, 3.43 g of SiO2, and 50.0 g of H2O,
then applying into the solutions.

In the next step, the prepared reaction gel was continually stirred at room temperature for 24 hours,
then the hydrothermal crystallization was performed by the microwave technique. Since heating is
known as a driving force of the crystallization process, the fundamental step in the synthesis is the
application of conventional or microwave heating. Normally, in the conventional hydrothermal
crystallization process, the heating process was conducted at 60 °C for 4 days in a shaker with a
rotation rate of 250 rpm, meanwhile in the crystallization process by using microwave heating, the
temperature was arranged of 90–130 °C for 15–240 min. We get the products by centrifugating it, then
washed it with de-ionized water until the pH value reached below 8, and for further characterization
dried at room temperature for 24 h.

The microwave equipment used in this study was a commercial microwave oven (CE1110C, Samsung,
Korea) with 900 W output power at a wavelength of 2.45 GHz. The oven was equipped with an
electronic system in order to accurately control the crystallization temperature. The control system
provided pulsed microwave pumping by switching the magnetron, externally. The temperature inside
the chamber was continuously measured by a Teflon coated thermocouple and adjusted by a
temperature controller (TC4Y, Autonics, Korea) with a precision of ±0.01 °C. A schematic diagram is
showned below8.

8
M. Ansari et., Preparation and characterization of nano-NaX zeolite by microwave assisted hydrothermal
method, Advanced Powder Technology al (2013), http://dx.doi.org/10.1016/j.apt.2013.10.021
10
 Figure 3 Microwave scheme

In the process, the microwave equipment using the time controller and the temperatur controller to
control the temperature during the crystallization process since the effecting of temperature to the
crystallization is important.

The sample is containing in the autoclave, this is the place where the crystallization happened under
the pressure and temperature controlling condition. The magetron generates microwave source that is
necessary microwave radiation for heating process and the contactor play a role as the device that
controls the electrical current to the magnetron, allowing for the switching on or off of the microwave
energy.

CHAPTER 2: EXPERIMENT
2.1. Equipment and materials
 Rice Cooker: Used as a high-frequency heating source.
 Magnetic Stirrer: To ensure proper mixing of the reactants.
 Measuring Balance: For precise measurement of raw materials.
 Glassware: Including beakers, flasks, and test tubes for reaction setup.
11
  pH Meter: To monitor and adjust the pH levels during synthesis.
 Microwave-Resistant Containers: For containing the reaction mixture.
 Oven or Furnace: For calcining the synthesized zeolite.
 Rice Husk Ash: A source of silica.
 Aluminum Hydroxide: For providing alumina in the reaction.
 Sodium Hydroxide (NaOH): Serves as an alkali.
 Distilled Water: For preparing solutions and suspensions.
 Additives (optional): Depending on the desired properties of the zeolite, materials like salts or
surfactants may be included.
2.2. Procedure
Preparation of Raw Materials
Rice Husk Ash Preparation: Burn rice husks at a controlled temperature to obtain ash rich in silica
(SiO2). Ideally, the ash should have a SiO2 content of 85-98% after burning.In Solution Preparation:
Dissolve a predetermined amount of sodium hydroxide (usually around 1M to 3M) in distilled water to
create a basic solution.Next is Mixing step: In a mixing container, combine the rice husk ash and
aluminum hydroxide with the sodium hydroxide solution. Stir using a magnetic stirrer to ensure
uniform distribution.
2.3. Microwave Irradiation
Loading the Mixture: Transfer the homogeneous mixture to a microwave-resistant container and place
it into the rice cooker.
Setting Conditions: Set the rice cooker to high frequency (microwave mode) and heat the mixture at a
predetermined temperature (generally between 80°C to 120°C) for a specific duration (15 minutes to 1
hour). The operating time and temperature can be modified based on preliminary experiments to
optimize zeolite formation.
Monitoring: Monitor the temperature and ensure consistent mixing throughout the heating period to
prevent localized overheating and ensure even synthesis.
2.4. Cooling and Filtering
Cooling:After the microwave treatment, allow the mixture to cool down to room temperature.
Washing: Rinse the produced zeolite slurry with distilled water to remove excess alkali and unreacted
materials. Use a filter to collect the precipitated zeolite crystals.
Drying: Dry the obtained zeolite under ambient conditions or in an oven at about 100-120°C until
constant weight is achieved.
Calcination Calcination Step: The dried zeolite is then calcined in a furnace at temperatures around
550°C for 2-6 hours. This step helps in improving the crystallinity and removing any organic
impurities.
Characterization:The final zeolite product can be characterized using techniques such as X-ray
diffraction (XRD) and Scanning Electron Microscopy (SEM) to confirm its structure and
morphological characteristics.

12