DISSERTATION PROPOSAL ON

DEVELOPMENT AND CHARACTERIZATION OF ZEOLITEY FROM A

NIGERIAN LOCAL RAW MATERIAL

BY

ORDU SAMUEL UWAJI.

G2023/MEM/EMP/ENG/FT/101

MASTERS IN ENGINEERING MANAGEMENT

FACULTY OF ENGINEERING

UNIVERSITY OF PORT HARCOURT.

SUPERVISOR: DR C. S. ESOBINENWU

APRIL, 2025

1
 CHAPTER ONE

INTRODUCTION

1.1 Background to the Study

Zeolites are crystalline, microporous aluminosilicate materials with three-dimensional, fully

crosslinked open framework structures that create uniformly sized pores at the molecular

level. These materials have garnered significant industrial, scientific, and academic interest in

various fields such as ion exchange (including liquid waste treatment, detergent

manufacturing, and radioactive waste storage), petroleum refining and petrochemical

production, coal processing, and fine chemical industries (Breck, 1980; Chiang & Chao,

2007; Xu et al., 2013). They are also widely utilized in separation processes, including

purification, drying, and environmental treatment. The versatility of zeolites as multi-

functional materials in various industrial applications is attributed to their intrinsic properties,

including uniform pore size and shape, catalytic activity, mobile cations, and

hydrophilicity/hydrophobicity (Adefila & Olakunle, 2014). The pore size of a zeolite is

crucial for adsorbing molecules of varying sizes, functioning as a molecular sieve. As a

result, zeolites selectively adsorb molecules that fit within their pore size, while molecules

larger than the pore diameter are excluded from adsorption.

Zeolite synthesis is traditionally carried out through a hydrothermal crystallization method, utilizing commercial

chemicals as sources of silica and alumina (Barrer, 1982). Commonly used chemicals in this process include

sodium aluminate, sodium metasilicate, silica gel, tetraethylorthosilicate (TEOS), and aluminum hydroxide.

However, these chemicals are typically costly, and their production processes are complex, resulting in high

production costs for zeolite, which restricts its widespread commercialization (Yaping et al., 2016) and limits its

applications in various industries

The use of affordable and widely accessible materials, such as kaolin, as a combined source

of silica and alumina is highly advantageous. The conversion of kaolin into zeolite through a

Metakaolinization process has been documented in previous studies (Chandrasekhar, 1996;

2
Chandrasekhar & 1999; Bosch et al., 1983). However, the significance of this research lies in

the fact that the composition of kaolin varies depending on its geographical origin (Bergaya

& Ligaly, 2016). The utilization of Elefun Nigerian kaolin (ENK) for zeolite production is

particularly beneficial for the industrial growth and development of Nigeria.

1.2 Statement of the Problem

The economic progress of a nation depends on effectively utilizing all of its available

resources. Kaolin clay, the primary raw material for the production of Zeolite Y, is abundant

in certain regions of Nigeria, including Elefun in Ogun State. However, despite this local

availability, the country continues to import Zeolite Y.

Zeolite Y is primarily utilized as a catalyst in the fluid catalytic cracking (FCC) unit of a

refinery, where it facilitates the conversion of larger, more complex hydrocarbons into

simpler and more valuable compounds.

Nigeria, possessing significant oil reserves estimated at approximately 36.2 billion barrels,

operates four refineries with a combined capacity exceeding 450,000 barrels per day. The

country consumes about 1,600 tonnes of zeolite catalysts daily, with an annual importation

totaling over 500,000 tonnes, amounting to a cost exceeding five billion Naira (Awe, 2016).

Additionally, the political ramifications for national industrial growth become evident,

particularly during periods of international sanctions, war, or political unrest. Consequently,

there is an immediate necessity to establish domestic capacity for the production of zeolite Y

catalysts.

1.3 Aim and Objectives

This research aims to synthesize Zeolite Y from clay sourced from the Elefun Local

Government Area in Ogun State, Nigeria. The study will involve characterizing the

synthesized zeolite and evaluating its catalytic performance by using it to crack cyclohexane

in a laboratory-scale fixed-bed reactor employing a pulse technique.

3
 The objectives of this research are as follows:

1. To determine the optimal conditions for synthesizing Zeolite Y from Elefun Nigerian kaolin.

2. To set up the necessary equipment for conducting the microcatalytic study of cyclohexane

cracking.

3. To identify the optimal conditions for cyclohexane cracking using the synthesized Zeolite Y.

1.4 Scope of the Study

The scope of this study was confined to the following:

(a) The development of Zeolite Y from Elefun clay.

(b) The conversion of the synthesized Zeolite Y into its hydrogen form.

(c) The performance testing of the developed catalyst using cyclohexane and gas oil, with

commercial Zeolite Y catalyst serving as a reference.

(d) The characterization of the materials through XRD, XRF, FTIR, SEM, BET surface area

analysis, and gas chromatography.

1.5 Justification of the Study

In response to the challenges outlined above, the utilization of local raw materials by

Nigerian industries gained significant attention in the early 1980s. This shift in focus was

prompted by the vulnerability of the Nigerian economy, particularly the manufacturing

sector, which was exacerbated by the global recession that disrupted the importation of raw

materials. As a result, the concept of sourcing raw materials locally was conceived. Nigeria is

endowed with substantial reserves of oil, gas, and solid minerals such as kaolin, which could

be leveraged for the country’s development. Currently, the Nigerian National Petroleum

Corporation (NNPC) depends on the importation of Zeolite Y catalysts for use in the oil and

gas processing at the fluid catalytic cracking units of its refineries. In mid-2010, Zeolite Y

was priced at US$5 per kilogram, but within just seven months, inflation caused the price

4
to skyrocket to US$140 per kilogram (Awe, 2018). With four refineries across the country

and a total processing capacity of over 450,000 barrels per day, NNPC consumes

approximately 1,600 tonnes of Zeolite catalysts daily, leading to an annual expenditure of

over 5 billion Naira for the importation of around 500,000 tonnes of Zeolite Y catalyst.

Moreover, additional refineries are expected to emerge from the ongoing refinery and

petrochemical projects in the country. These include:

(a) The Escravos Gas to Liquids (GTL) project, a joint venture between NNPC, Chevron

Nigeria, and SASOL of South Africa. The initial capacity of the project is 34,000 barrels per

day, with plans for expansion to 120,000 barrels per day within ten years. Zeolite Y is the

preferred catalyst for the GTL processes (Ahmed et al., 2020).

(b) The NNPC-Chinese Refinery Agreement aims to establish three Greenfield refineries and

a petrochemical plant in Nigeria, with the first refinery scheduled to be commissioned in

Lagos in 2016, having a capacity of 350,000 barrels per day. Similar to other modern

refineries, the plant will primarily utilize Zeolite Y catalysts.

(c) The Federal Government of Nigeria has entered into a memorandum of understanding

with two US-based companies to build modular refineries with a total capacity of 180,000

barrels of crude oil per day (Daily Trust, 25/9/2012).

(d) In April 2013, Nigerian business magnate Dangote revealed plans to inaugurate a refinery

with a capacity of 400,000 barrels per day at the Olokola Free Trade Zone, located on the

Gulf of Guinea near Lagos, by 2016. This refinery, like the others, will require Zeolite Y. As

production increases, the demand for Zeolite Y catalysts will rise, consequently leading to

higher expenditure on its importation (Ahmed et al., 2020).

The synthesis processes and conditions for Zeolite Y from imported clays are well-

documented (Barrer, 2016; Zhdanov, 1971, 1977; Aderemi, 2006), however, there is limited

research on utilizing Nigerian kaolin clays as raw materials for zeolite production. It has been

5
established that the characteristics of the raw materials, such as crystallinity and composition,

significantly influence the properties of the final zeolite product (Breck, 1980; Aderemi,

2006; Ajayi, 2018). Hence, a thorough examination of the behavior of locally sourced kaolin,

such as Elefun kaolin from Ogun State, Nigeria, is essential. This research aims to gather

vital data to support the development and production of Zeolite Y within Nigeria.

This project would also help to conserve foreign reserves and create employment for our

teeming youth.

6
 CHAPTER TWO

LITERATURE REVIEW

Zeolites were first discovered as naturally occurring minerals nearly 200 years ago, though

today, they are predominantly synthesized in laboratory settings, as will be discussed in this

study. Initially, zeolites were found in the cavities of basalt rock, later extending to

sedimentary rock closer to the Earth's crust. Their formation is believed to have resulted from

various natural processes occurring within the Earth's crust, which include:

 Deposition from low-temperature alteration of marine sediments

 Crystal formation due to hydrothermal interactions between solutions and basaltic lava flows

 Volcanic deposition on alkaline soils

 Volcanic sediment deposition within closed alkaline and saline lake systems

 Formation due to groundwater activity on volcanic minerals

 Creation as a result of low-grade burial metamorphism

Stilbite, the first natural zeolite, was discovered in 1756. Currently, there are approximately

36 known natural zeolites (Table 2.1), all of which have distinct structures and specific

applications. These natural zeolites typically possess a low to medium silica-to-alumina ratio,

which limits their industrial applications when compared to synthetic zeolites. Their primary

use is in ion exchange processes, particularly in the treatment of radioactive materials (e.g.,

clinoptilolite). They also find applications in agriculture and as adsorbents (e.g., MOR)

(Carrado & Garwood, 2009).

Table 2.1: Some known natural zeolites with their codes and years of discovery

(Breck and Flannigan 1980).

NO NAME YEAR OF CODE USED BY IZA

DISCOVERY
1 Stilbite 1756 STI
7
2 Natrolite 1758 NAT
3 Chabazite 1772 CHA
4 Harmotome 1775 -
5 Analcime 1784 ANA
6 Laumontite 1785 LAU
7 Heulandite 1801 HEU
8 Scolecite 1801 -
9 Thomsonite 1801 THO
10 Gmelinite 1807 GME
11 Mesolite 1813 NAT
12 Gismondine 1816 GIS
13 Brewsterite 1822 BRE
14 Epistilbite 1823 EPI
15 Philipsite 1824 PHI
16 Edingtonite 1825 EDI
17 Herschelite 1825 -
18 Levynite 1825 LEV
19 Faujasite 1842 FAU
20 Mordenite 1864 MOR
21 Clinoptilolite 1890 HEU
22 Erionite 1890 ERI
23 Offretite 1890 OFF
24 Kehoeite 1893 -
25 Gonnardite 1896 NAT
26 Dachiardite 1905 DAC
27 Stellerite 1909 STI
28 Ferrierite 1918 FER
29 Viseite 1942 -
30 Yugawaralite 1952 YUG
31 Wairakite 1955 ANA
32 Bikitaite 1957 BIK
33 Paulingite 1960 PAU
34 Garronite 1962 GIS

8
 35 Mazzite 1972 MAZ
36 Merlinote 1974 MER
37 Barrerite 1974 STI

2.2 Structure and Nomenclature of Zeolites

The representation of a typical zeolite by its primary building unit is TO4 where T is

the framework atom as shown in Figure 2.1.

Figure 2.1 The primary building unit TO4 of zeolite-Y ([Link]/zeolite,2009).

The water molecules and cations within the zeolite framework are mobile, with water being

capable of being reversibly removed at temperatures ranging from 100°C to 500°C during

dehydration. The stability of the zeolite structure typically extends up to temperatures

between 700°C and 800°C (Dyer, 2004).

9
Figure 2.2 Existing secondary Building Units (SBUs) in zeolite Framework
([Link], 2016)

2.3 Pore Structure

Based on this classification, zeolites exhibit three principal pore opening types: small pores

composed of 8-membered rings, such as those found in zeolite A and erionite; medium pores

with 10-membered rings, as observed in ZSM-5; and large pores with 12-membered rings,

typical of zeolite X and zeolite Y. A representative illustration of the primary pore system in

zeolite Y is provided in Figure 2.3.

Figure 2.3: 12- ring Pore structure of zeolite Y studied in this research [IZA, 2012]
10
2.5 Properties of Zeolites

2.5.1 Ion- exchange

2NaZ+CaCl2 CaZ2 + 2NaCl (2.2)

Where Z is the zeolite.

2.5.2 Catalysis

Figure 2.5: Bronsted acid site in zeolites (http [Link], 2012)

2.5.3 Adsorption

The mechanisms involved in adsorption include:

(a) Equilibrium selective adsorption

(b) Rate selective adsorption

(c) Shape selective adsorption

(d) Ion exchange

(e) Reactive adsorption.

2.6 Application of Zeolites

A variety of catalytic applications of zeolites are summarized in Table 2.2.

11
Table 2.2: Zeolite structure type used in commercial and emerging catalytic
processes (Dyer, 1988, Weikamp and Puppe, 199)

Zeolite type Catalytic processes

FAU(Y) Catalytic cracking, hydrocracking, aromatic

alkylation,
MON(mordenite) NOX reduction, acetyiation

MFI(ZSM-5, TS-1 and silicalite) Light alkane hydroisomerization, hydro

cracking, dew axing, NOX reduction,
Aromatic alkylation and
BEA (beta) Dewaxing, methanol to gasoline, methanol
to olefin and product, FCC addictive,
hydrocracking, olefin
LTL(KL) Benzene alkylation, aliphatic alkylation,
Acetylation
MWW(MCM-22) Baeyer Villiger reaction, FCC additive,
etherification
CHA(SAPO-34) Alkane aromatization Benzene alkylation
Methanol to olefin Long chain Alkane
hydroisomerization,
AEL(SAPO-1) RHO (Rho) Beck mann re- arrangement Amination

TON(ZSM-22) Long chain alkene hydroisomerization

12
Table 2.4: Locations of Kaolin Deposit in Nigeria. (Onaji and Ahmed, 2001)

Clay Location (State) Al2O3 Si2O3 Fe2O3 CaO+MgO LOI Refractoriess

% % % % (PCE)
Cone Equiv.
o
No T C
Alkaleri Bauchi 25.43 54.30 1.05 1.00 15.73 33.5 1740
Onibode Abeokuta(Ogun) 39.30 42.30 Trace 1.05 14.20 >34 >1740
Elefun Abeokuta (Ogun) 37.0 53.80 2.57 0.30 0.69 33 1730
Oshiele Abeokuta (Ogun) 28.30 53.40 1.35 0.88 15.00 33 1730
Orun ” ,, 34.55 50.55 2.05 1.10 15.50 33 1730
Ozubulu Nnewi 19.31 58.30 1.55 1.25 14.16 32 1710

Enugu Enugu(Enugu) 22.71 55.00 2.42 1.95 16.35 29 1650

Nsu Okigwe(Imo) 30.22 50.60 1.90 1.08 10.54 32 1710
Okpekpe Auchi (Edo) 24.30 53.20 1.45 1.30 16.86 29 1650
Kankara Kankara(Kastina) 38.64 44.50 Nil 1.30 16.70 34 1760
Giro Giro(Sokoto) 38.72 43.54 2.10 1.48 14.00 34 1760
Warram Warram(Plateau) 37.13 43.54 1.15 0.58 14.20 34 1760
Sabon Jos(Plateau) 25.88 25.32 13.10 3.20 18.36 27 1610

Ukpor Nnewi 33.20 48.00 1.20 0.73 12.12 33 1730

Ifon Ifon (Ondo) 36.80 47.90 0.67 1.11 12.32 33 1730

Oza Oza 38.07 46.00 0.78 0.23 13.7 33 1730

Nagoga Nagogo(Edo)

13
2.8 Synthesis of Zeolites

The formation of these zeolitic structures is governed by multiple factors, notably elevated temperature and

pressure conditions. The formation of zeolites can span thousands of years or more, with early-formed zeolites

such as clinoptilite and philipsite being metastable. These are eventually converted into more stable forms like

analcime and heulandite. While millions of tonnes of natural zeolites are produced annually, advances in

laboratory synthesis have also significantly improved (Barrer, 1983).

A reaction scheme can also be presented for zeolite crystallization from the system of

Na2O-Al2O3-SiO2-H2O showing the gel preparation and crystallization:

NaOH (aq) + NaAl (OH)4(aq) + Na2SiO3(aq) T1 ≅ 25oC

[ Naa(AlO2)b (SiO2)c . NaOH.H2O] gel T2 ≅ 25 to 100℃

Nax[(AlO2) x (SiO2)y].mH2O + solution

2.8.1 Zeolite crystals

Various types of autoclaves and reactors are also employed in the synthesis of zeolites. A

standard procedure for the hydrothermal synthesis of zeolites, as outlined by Barrer (1984)

and Mintova et al. (2008), involves mixing source materials, usually in a strongly basic

environment, and stirring to create a homogeneous gel. The gel is then aged under specific

conditions before undergoing crystallization in a sealed autoclave at a designated temperature

and for a set period. The zeolite is typically recovered by washing and drying.

14
Figure 2.9: The Teflon-lined stainless steel autoclave used in this work

15
2.8.2 Zeolite Y synthesis starting components

The primary reactants involved in the synthesis process, as discussed by Breck (1980), Xu et

al. (2013), Auerbach (2009), Dyer (1994), and Kovo (2016), include:

 Silicon source

 Aluminium source

 Metal ion

 Base

 Mineralizer

 Water

 2.8.3 Crystallization of zeolite

 The crystallization process plays a crucial role in the synthesis of zeolite Y, as it

involves a condensation reaction between silicate and aluminate in a strongly basic

solution. This process can be broken down into two main stages: nucleation and

crystal growth.

 (a) Solid Hydrogel Transformation: The solid hydrogel transformation mechanism

 (b) Solution Mediated Transport Mechanism
 (c) Dual-phase Transition Mechanism: The dual-phase transition mechanism was

2.9 Catalytic Cracking

2.9.1 Catalytic cracking processes

The main types of catalytic cracking processes are fixed bed process (Fig 2.10) and the

moving bed process (Fig 2.11)

16
Figure 2.10: The Houdry fixed bed process (Shell international, 2004)

Figure 2.11: The fluid catalytic cracking process (NNPC, 2019)

17
2.9.2 Cracking reaction

This study focuses exclusively on catalytic cracking, with its specific mechanisms and

characteristics detailed in the subsequent sections.

R-CH=CH-CH3 + HY -» R-CHrCH -CH3 +HY

(2) Hydride Ion Abstraction: In this mechanism, a stable hydrocarbon—typically a paraffin

—interacts with a Lewis acid site (L) on the catalyst surface. The reaction advances through

the removal of a hydride ion (H⁻) from the paraffin molecule, resulting in the formation of a

positively charged carbonium ion intermediate.

R-CH2-CH2-CH3 + HY -» R-CH2-CH -CH3 +HY

(3) Electron Abstraction: In this pathway, a neutral hydrocarbon species undergoes the

removal of an electron, leading to the generation of a carbonium ion (R ⁺). This ion then

propagates the reaction by interacting with another paraffin molecule in a chain reaction

mechanism. During this process, a hydride ion (H⁻) is transferred from the new paraffin to

the carbonium ion, producing a new paraffin and regenerating a fresh carbonium ion.

R–CH₂–CH₂–CH₃ + R⁺ → R–CH₂–CH⁺–CH₃ + RH

Table 2.5 Comparison of Catalytic and Thermal Cracking Products.

Hydrocarbon Thermal cracking Catalytic cracking

n-Hexadecane (Cetane) Major product is C2 with Major product is C3 to C6.

large amount of C1 and C3 few n-a-olefins above C4.
and C4 to C15 n-α-olefins. Aliphatics mostly branched.
Few branch aliphatics.

Aliphatics Small amounts of aromatics Large amounts of aromatics

0 0
formed at 500 C. formed at 500 C.
Alkylaromatics Crack within side chain. Crack next to ring.

n-Olefins Double bond shifts slowly. Double bond shifts rapidly.

Little skeletal isomerization. Extensive skeletal
isomerization.

18
 Olefins Hydrogen transfer is a Hydrogen transfer is an
minor reaction and is important reaction and is
nonselective for tertiary selective for tertiary olefin.
olefin.
Crack at much higher rate
Cracking is about same rate than corresponding paraffins.
as corresponding paraffins.

Naphthenes Crack at lower rate than Crack at about same rate as

paraffins. paraffins with equivalent
structural groups.
Source: Greenfelder, 1955
2.9.3 The mechanism of catalytic cracking

Step 1: Carbonium Ion Formation

Step 2: Rearrangement Toward Stability

Step 3: Beta Scission of the Carbonium Ion

2.9.4 Catalytic Cracking of Alkylaromatic Hydrocarbon

The catalytic cracking of aromatic hydrocarbons is characterized primarily by the

pronounced stability of the benzene ring and the highly selective cleavage of alkyl

substituents from alkylated benzenes. Cracking becomes increasingly favorable as the alkyl

chain lengthens, while the selectivity of cleavage remains high—evidenced by consistently

significant benzene yields.

Two mechanistic pathways have been proposed for the formation of carbonium ions as

intermediates. The first, suggested by Thomas (1955), involves the direct protonation

mechanism. In this route, a proton from the acidic site of the catalyst is directly added to one

of the π-bonds within the aromatic ring, generating a carbonium ion. Subsequent bond

cleavage then occurs specifically at the HY position on the positively charged carbon atom of

the intermediate.

19
The alternative mechanism, proposed by Greenfelder (1955), suggests that due to the high

proton affinity of the benzene ring, the dealkylation process proceeds as a simple exchange

reaction. In this mechanism, the aromatic ring replaces an alkyl carbonium ion with a proton,

facilitating the cleavage of the alkyl group while preserving the integrity of the benzene ring

structure:

Consequently, the degree of dealkylation is governed by how readily alkyl carbonium ions

can be generated. For instance, the formation of a methyl carbonium ion is highly

unfavorable, making toluene notably resistant to decomposition under catalytic cracking

conditions.

2.10 Kinetics of the Cracking Reaction

A kinetic reaction model involves the adsorption of a single hydrocarbon molecule A onto an

active site on the catalyst surface, followed by the cracking of the adsorbed molecule to

produce products B and C.

A B + C
If the reaction is a first order with respect to A, the reaction rate is

-rA = - = kCA = kCA0(l-XA) 2.10.1

20
Where
CA is the adsorbed phase concentration (mol/gm).

CAo is the initial adsorbed phase concentration (mol/gm). XA is the fraction of A

converted to products,

k is the reaction rate constant.

- rA is rate of reaction based on unit mass of catalyst (mol/gm. sec).

For a steady state plug flow system:

FA0 dXA = -rA dW 2.10.2

21
Where

FAO is the molar flow rate of A entering (mol/sec). W is the mass of the catalyst (gm).

Rearrangement gives:

Since the molar flow rate of A entering is constant, FAO can be taken out of the integration and

from the reaction rate - rA (which is then a function of X), we may write:

or

2.10.3

The above equation is used to find the reaction rate constant at different temperatures and from

the Arrhenius' Law:

k = ko exp 2.10.4

or

lnk = ln k0 - 2.10.5

Where k0 is the frequency factor.

E is the activation energy of the reaction.

R is the gas law constant.

T is the absolute temperature.

A plot of ln k versus 1/T will give the value of the activation energy of the cracking reaction.

22
 CHAPTER THREE

MATERIALS AND METHODOLOGY

Elefun clay was sourced and processed through refinement stages, including beneficiation and

calcination, before being used in the formulation of zeolite samples. The prepared samples were

carefully monitored at each stage, with analyses conducted using advanced techniques such as

X-ray fluorescence (XRF), X-ray diffraction (XRD), and scanning electron microscopy (SEM).

Additional characterization methods were also employed to identify the crystallite type and

evaluate other relevant properties. These methodologies are described in detail in the relevant

section of the work.

3.1 Materials

(a) Kaolin source from Elefun Local Government Area of Ogun State.

(b) Reagents

In carrying out this experiment, the listed materials and equipment were used.

3.1.1 Beneficiation Equipment/Material

Table 3.1: List of Materials/equipment used during Beneficiation

Equipment/Material Source Quantity/Model

Raw Elefun Kaolin Elefun, Ogun State 4kg

Plastic bucket 20 litres (4 nos)

Sieve 75μm mesh

No. 64 Michem instrument

3.1.2 Calcination Equipment/Materials

The equipment/materials used for calcination of Elefun kaolin are presented in Table 3.2

23
Table 3.2: List of Materials/Equipment used during Calcination

Equipment/Material Source Quantity/Model

Locally fabricated crucible 0.5litre (5nos)

Electric furnace No: LH120/14m/temp

1400, 400v, 50/60Hz,

26.0A, 18.0kw

Desicator with silica gel Nr/No 182487

24
3.1.3 Dealumination Material/Equipment

The equipment/materials used in carrying out dealumination of metakaolin are presented in

Table 3.3.

Table 3.3: List of Materials/equipment used during Dealumination

Equipment/Material Source/Manufacturer Quantity/Model

Metakaolin 2kg

Electronic weighing PW 184, M:180g -

machine accuracy 10-4g

Heating mantle with voltage Addis Chemical, Zari 500ml capacity

Sulfuric acid (H2SO4) 250ml of Silfuric Acid

(96% w/w)

Three neck-round bottom Edward England 1 set

flask, thermometer and

reflux condenser

Vacuum pump

pH meter No: ES001

25
3.1.4 Gelation material/equipment

Table 3.4: List of Materials/equipment for Gel formation and actual synthesis of zeolite Y

Equipment/Material Supplied By Quantity/Model

Dealuminated metakaolin 2kg
with Si/Al molar ratio of
4.49
Electronic weighing Addis Chemical, Zaria PW 184, M:180g
machine accuracy 10-4g, 500ml
capacity
Sodium hydroxide (NaOH) ABU, Mkt 200g, 96% w/w
Deionized water ABU, Zaria 20 litres
1 litre Plastic cup for aging 2 nos
Electrically driven magnetic No: ES001
stirrer
Vacuum pump ABU, Zaria
pH meter
Laboratory oven ABU, Zaria Model No:MD6C-64,
Michem Instrument
Teflon/polyethylene 6 nos
Standard zeolite Y KRPC 1kg

26
3.1.5 Chemicals Used for Performance Test Experiment

The chemicals used for this study are listed in Table 3.5.

Table 3.5: List of Chemicals used during performance test experiment

Material Manufacturer Comment

Locally developed zeoliteY Si/Al molar ratio of 4.49

Commercial zeolite Y Grace Gmbh USA Si/Al molar ratio of 5.70

Catalyst

Cyclo-Hexane Johan Hattermann 99.99% purity

Vacuum Gas Oil NNPC/KRPC, Kaduna Supplied by KRPC

Nitrogen gas NNPC/KRPC Supplied by KRPC

Silica Gel BDH Chem. Poole 6-20 mesh

England

Copper Oxide Hopkin & Williams Assay 90.0% min.

27
3.1.6 Equipment Used for Performance Test Experiment

The equipment used in the research work is presented in Table 3.6.

Table 3.6: List of Equipment used during Zeolite Y catalyst performance test

Equipment Make Comment

Gas Chromatograph and Supplied by KRPC
accessories
Electronic Weighing OHAUS, U.S.A. Supplied by KRPC
Balance
Electronic Stop Watch Not Available Supplied by KRPC
Gas Cylinder and Unknown Supplied by KRPC
Regulators
Temperature Reading Meter Shinohara Ltd Purchased from Power-link
Electrical, Kaduna
Rheostat Purchased at Kaduna
Split Valve Purchased at Kaduna

Control Valves Valco instrument Purchased at Kaduna

Tubular Oven + Purchased at Kaduna
Thermocouple
Flow Meter Purchased at Kaduna
Stainless Tube (6mm int. Owode-Onirin, Lagos, Nig.
diameter)
Glass Wool
Teflon Tape Purchased at Iyana,Otta

28
Methodology of Zeolite Y synthesis from Elefun clay and its performance test

Raw Elefun Kaolin

↓
Kaolin Beneficiation
↓
Drying at Room temp (34oC) for 48Hrs
↓
Calcinations at 850 oC for 6Hrs
↓
Characterization
↓ (XRF, XRD, FTIR, SEM, BET)
Dealumination using Novel and conventional method
↓
Geletion using various Na2O/SiO2 (0.6 – 0.8)
↓
Ageing for Curing using 7 days, 9days
↓
Crystallization at 100 oC for 24Hrs
↓
Zeolite NaY

Figure 3.1: Flow Diagram of Zeolite Y Synthesis from Elefun Clay

3.2.1 Clay Beneficiation

Clay beneficiation involves the enhancement of both the physical and chemical attributes of

crude kaolin. The procedure encompasses the following stages:

• Chemical and mechanical dispersion of the raw kaolin ore

• Screening and sieving to eliminate physical contaminants such as sand and mica

• Selective flocculation and flotation techniques to remove impurities responsible for

discoloration

29
• Centrifugation using solid bowl and/or disc nozzle centrifuges to regulate particle size

distribution

• Chemical flocculation and leaching to solubilize iron content and to condition kaolin slurries

for subsequent dewatering

• Particle size reduction employing dry milling equipment such as cage mills, roller mills, and

high-speed pulverizers

• Dewatering operations utilizing hydro separators, rotary vacuum filters, and both rotary and

vertical calciners

A total of 4 kg of raw kaolin obtained from Elefun Local Government Area in Ogun State was

immersed in a 20-litre plastic container filled with tap water to approximately three-quarters (¾)

of its capacity. The suspension was left to soak for a duration of seven days. Every six hours, the

kaolin slurry was subjected to mastication and vigorous agitation using a high-speed, three-blade

mechanical stirrer to ensure thorough dispersion. Following complete sedimentation of the

kaolin, the floating impurities along with the supernatant liquid were carefully decanted. The

intensive mastication of the kaolin facilitated the separation of stony impurities, which were

eliminated either manually by handpicking or through slurry decantation. Subsequently, clean

water was added to the muddy kaolin to induce frothing via agitation, allowing for stratified

sedimentation. This was followed by repeated pulping cycles involving mastication, grinding,

crushing, agitation, and decantation, continued until no discernible solid deposits were observed

at the bottom of the container. The uppermost layer of the resultant slurry was carefully

extracted and transferred into a separate vessel, where it was washed thoroughly and passed

twice through a 75-micron mesh sieve. The sieved slurry was then dewatered and air-dried for

30
48 hours under ambient conditions, followed by oven drying at 45°C for 4 hours using an

electric oven (Model No: MD6C-64, Michem Instrument). The dried solid was subsequently

pulverized using a ball mill to achieve a fine particle size, after which the processed sample was

packaged for further analysis.

3.2.2 Calcination

Calcination is employed to transform the beneficiated clay into a more reactive form known as

metakaolin, a semi-amorphous phase. This conversion is necessary because natural kaolin

exhibits low reactivity and tends to form hydrosodalite upon interaction with sodium hydroxide

(Chandrasekhar & Pramada, 2005). Literature reports suggest that the optimal calcination

temperature typically falls within the range of 600°C to 900°C, with calcination durations

spanning from 1 to 8 hours (Yaping et al., 2014; Liu & Pinnavaia, 2010).

The transformation of kaolin into metakaolin, known as metakaolinization, is characterized by

the elimination of hydroxyl groups, accompanied by a structural reorganization wherein the

octahedral layers convert into a tetrahedral framework during calcination (Murat et al., 1998;

Klinowski & Joao, 1996). As an aluminosilicate, kaolin contains Al³ ⁺ ions that may exist in both

tetrahedral (IV) and octahedral (VI) coordination states. However, for successful zeolite

synthesis, it is critical that the Al³⁺ ions be present in the tetrahedral coordination. Thus,

generating an amorphous metakaolin structure with predominantly IV-coordinated aluminum is

a fundamental requirement for effective zeolite production from kaolin (Chandrasekhar, 2002;

Patrylak et al., 2007).

The thermal transformation of kaolin during furnace heating has been extensively documented

and is known to offer several technological advantages (Breck, 1980; Madani et al., 1996). This

sequence of reactions leads to the formation of a highly disordered phase known as metakaolin,

31
typically produced within the temperature range of 550–900°C during calcination, as illustrated

in Equation 3.1.

2Al2Si2O5(OH)4 2Al2Si2O7 + 4H2O 3.1

Metakaolin On further heating, a new phase is obtained at around 925oC called spinel, a
defected Alumina-silica structure

2Al2Si2O7 Si3Al4O12 + SiO2 3.2

Spinel
o
While mullite and cristobalite are formed at a temperature of 1050 C
3Si3Al4O12 2Si2Al6O13 + 5SiO2 3.3
Mullite

This study focuses on the transformation of Elefun-sourced kaolinite clay into metakaolin

through a novel, rapid dehydroxylation technique that is both highly reactive and energy-

efficient. Based on the measured thermal conductivity, specific heat capacity, and thermal

diffusivity of the clay, it is recommended that only small batches of kaolin be subjected to

calcination at a time. Alternatively, the adoption of a rotary furnace is advised to enhance

thermal efficiency and uniformity during the process.

The optimal calcination temperature employed in this study was determined by evaluating the

influence of both temperature and duration on the degree of amorphousness, as well as the

solubility and reactivity of the kaolinite components in acid and alkali media. Parallel

investigations were conducted to identify the most effective metakaolinization temperature

capable of transforming alumina and silica into more reactive and readily digestible forms

suitable for zeolite synthesis.

Based on the outcomes of the preliminary investigations, the calcination temperature for the

beneficiated kaolin was set at 850°C. The thermal treatment was carried out using a

32
programmable electric furnace (Model No: LH 120/14), with the temperature ramped from

ambient conditions (34°C) to the target calcination temperature at a controlled rate of 10°C/min.

The material was maintained at 850°C for a duration of six hours, following the procedure

outlined by Babalola et al. (2020). Approximately 500 grams of the refined kaolin were evenly

distributed in a large, custom-fabricated rectangular crucible to ensure uniform heat exposure,

considering the low specific heat capacity and latent heat properties of kaolin. After calcination,

the resulting metakaolin was cooled in a desiccator before being subjected to further

characterization and application.

3.2.3 Dealumination of the Calcined Clay

To enhance the SiO₂:Al₂O₃ ratio in the base material, dealumination serves as a viable

alternative to the external incorporation of silica. In this study, the optimization of acid

concentration for efficient alumina leaching from the clay matrix was explored through a series

of preliminary tests. Specifically, 50 grams of the beneficiated clay were each treated with

149.6864 cm³ of sulfuric acid (H₂SO₄) at a concentration of 60% (w/w). The corresponding

dealumination (acid leaching) reaction is represented as:

Al2O3(s) + 3H2SO4(aq) Al2(SO4)3(aq)+3H2O 3.4

Dealumination

The silica-to-alumina (Si/Al) ratio of the resulting metakaolin was evaluated through

compositional analysis utilizing X-ray fluorescence (XRF). Findings revealed that the intrinsic

Si/Al ratio of the metakaolin was insufficient for the synthesis of faujasite-type zeolite.

To meet the compositional requirements for synthesis, alumina and other impurities were

removed from the metakaolin through a dealumination process. This was achieved by reacting

the calcined kaolin with sulfuric acid. The dealumination reaction was carried out using a non-

33
heating method referred to as the "Novel Approach." The degree of dealumination was assessed

by varying the reaction times.

(a) Conventional Heating Method

This approach typically involves the use of an external thermal energy source to provide the

necessary kinetic energy for effective collisions and successful reactions between metakaolin

and sulfuric acid. In all instances, dealumination was carried out using three times the

stoichiometric amount of 60 wt% sulfuric acid to improve mass transfer and minimize the

formation of solid cake (Aderemi, 2006).

Approximately 50 g of metakaolin was combined with 83.86 cm³ of deionized water and

149.6864 cm³ of sulfuric acid in a three-necked round-bottom flask, with vigorous stirring. The

central neck of the flask, positioned on a heating mantle, was fitted with a reflux condenser,

while a thermometer was placed in the second neck, and the third neck was sealed with a rubber

cork. The reaction time was varied to 3, 6, 8, and 10 minutes to determine the optimal reaction

time for achieving a silica-alumina ratio between 3 and 10. A reaction time of 3 minutes yielded

the desired silica-alumina ratio and was subsequently selected for bulk production.

The dealuminated samples were extensively washed with hot deionized water to ensure the

thorough removal of excess unreacted acid and other soluble salts formed during the leaching

process. Following this, the samples were dewatered using a suction pump and then dried in an

oven at 110°C for 3 hours. Once dried, the dealuminated samples were packaged for further

analysis.

(b) Non-heating Method of Dealumination

34
This method of dealumination does not require an external thermal energy source to facilitate the

reaction. Instead, it utilizes the heat generated from the reaction between sulfuric acid and water.

A similar approach to that described in Section 3.3(a) was employed in this method.

The reaction time was varied between 3 and 11 minutes, with intervals of 2 minutes, to

determine the reaction duration necessary to achieve the desired silica-alumina ratio of 5. To

further explore the relationship between reaction time and the silica-alumina ratio, additional

reaction times of 17 and 21 minutes were also tested. Once the reaction period was complete, the

samples were quenched with water.

The dealuminated samples were thoroughly washed with deionized water to ensure the nearly

complete removal of any unreacted acid and other soluble salts produced during the leaching

process. They were then dewatered using a suction pump and left to dry in dust-free natural air

for 24 hours. The dried dealuminated samples were subsequently packaged for further analysis.

3.2.4 Gel Formation

At this stage gellation was achieved with a desired molar composition as shown in Equation

3.5 and 3.6

SiO2 = 4.695; Na2O = 0.6; H2O = 30 3.5

Al2O3 SiO2 Na2O

Na2O+H2O 2NaOH 3.6

The SiO2/Al2O3 ratio utilized in this study was derived from the compositional analysis of the

dealuminated samples, as presented in Table 4.3. Additionally, the ratios of sodium oxide to

silica (Na2O/SiO2) and water to sodium oxide (H2O/Na2O) were maintained at constant values.

For the gelation of 50g of dealuminated metakaolin, the required amounts of sodium hydroxide

(NaOH) and water were found to be 20.3g and 136.4 cm³, respectively. Comprehensive

35
calculations are provided in Appendix B. In the synthesis process, 50 g of dealuminated

metakaolin was combined with 136.404 cm³ of deionized water. The first half (68.2 cm³) of the

water was initially added to a 1-liter plastic container, into which the metakaolin was thoroughly

mixed. Subsequently, 20.3 g of sodium hydroxide pellets (96% purity) were added to the

mixture and stirred vigorously until completely dissolved. The remaining half of the deionized

water was then introduced, following the procedure adapted from Ajayi (2018), and the mixture

was agitated using an electrically powered stirrer for 4 minutes to form an aluminosilicate gel.

The resulting gel was then transferred into a polypropylene autoclave for the aging process.

3.2.5 Synthesis of Zeolite Y from Elefun Clay

The synthesis of Zeolite Y was conducted by evaluating the influence of aging duration,

crystallization time, and temperature. The prepared aluminosilicate gel was subjected to aging at

34 °C for durations of 7 and 9 days. This was followed by hydrothermal crystallization in a

laboratory oven at 100 °C for a period of 24 hours. Upon completion of the crystallization stage,

the autoclave was withdrawn from the oven, and the contents were filtered. The resulting solid

was washed thoroughly with deionized water until a neutral pH range of 7–8 was achieved. The

washed product was then dried completely and packaged for subsequent analyses.

Characterization of the synthesized zeolite products was performed using X-ray Diffraction

(XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy

(FTIR), and Brunauer–Emmett–Teller (BET) surface area analysis.

3.2.6 Determination of Ion Exchange Capacities

NaY(s) + NH4Cl2(aq) ↔ NH4Y(s) + NaCl

↓
Washing the slurry with de-ionized H2O

36
 ↓ Analysis (XRF,XRD,SEM,BET)
NH4Y(s)+ Bacl2 NH4Y + BaSO4
↓
o
NH4Y + Heat (450 C) HY + ↑NH3
↓
HY

Figure 3.2: Modification of Zeolite NaY to Zeolite HY

The synthesized product obtained from Section 3.4, identified as zeolite NaY, was subsequently

converted to its hydrogen form, referred to as zeolite HY. This transformation was accomplished

by subjecting 10 grams of NaY to ion exchange using 100 mL of 0.1 M ammonium chloride

(NH₄Cl) solution in a 1-liter plastic container. The mixture was vigorously stirred using a

magnetic stirrer for 10 minutes at ambient temperature. To ensure sufficient exchange of sodium

ions with ammonium ions, the procedure was repeated twice.

NaY(s) + NH4Cl(aq) → NH4Y(s) + NaCl 3.3

The resulting solid was subsequently separated from the slurry through filtration and thoroughly

rinsed with deionized water until it was confirmed to be free of chloride ions. To verify the

complete removal of chlorides, 50 mL of barium sulfate solution was introduced to the washed

sample. The absence of a barium chloride precipitate at the bottom of the container confirmed

that no residual chloride ions remained.

NH4Y (s) + Bacl2 NH4Y (s) + BaSO4. . 3.4

The resulting solid (NH₄Y) was air-dried at ambient temperature for 24 hours and subsequently

transferred into a crucible, then placed in a furnace set at 450 °C for a residence time of 4 hours.

37
During this thermal treatment, the ammonia was expelled from the NH₄Y structure, effectively

converting it into the hydrogen form of zeolite Y (HY).

HY + ↑NH3
o
NH4Y + Heat (450 C) → 3.5

The solid zeolite HY was allowed to cool and was packaged for analysis.

3.3 Performance Evaluation of Zeolite Y Synthesized from Elefun Kaolin

The catalytic performance of the synthesized zeolite Y derived from Elefun kaolin was evaluated

using a fixed-bed reactor, applying a pulse microcatalytic technique to crack cyclohexane.

The reactor system was custom-designed and fabricated in accordance with the design principles

outlined in Sections 2.10 and 2.11. For benchmarking purposes, a commercial zeolite Y catalyst

obtained from the Nigerian National Petroleum Corporation (NNPC) served as a reference. The

experimental setup comprised a microcatalytic reactor, a gas chromatograph, and an electric

heating unit. The reactor itself consisted of stainless steel tubing with a length of 0.05 m and an

internal diameter of 0.006 m, positioned within a cylindrical tubular furnace for uniform heating.

The system layout is illustrated in Figure 3.3.

Fig.3.3 Experimental Set-up

38
 Legend

1. High purity gas cylinders containing Helium as the carrier gas.

2. Cylinder regulator head for pressure regulation.

3. One-way control valves for the controlling of the carrier gas flow rate.

4. Silica gel bed for removal of traces of water.

5. Double way valve through which the removed water from (5) is flushed out.

6. Copper oxide bed for removal of oxygen.

7. Reactants injection point. The reactant is injected with the aid of a microsryinge and

needle.

8. Micro catalytic reactor, which is a combination of a stainless steel tube 0.05m long and

0.006m internal diameter in a horizontal furnace equipped with temperature control devices.

9. Condenser for cooling the product mixture.

10. Three-way valve, through which bubble-soap flow meter is connected.

11. Analytical Systems Gas Chromatography (Hitachi type fixed with FID, TCD).

The cracking setup was placed inside a tube furnace, with the temperature monitored using a

thermocouple. For each cyclohexane injection, a microsyringe was used to introduce the feed

into the reactor.

The stainless-steel reactor tube was charged with 0.15 g of catalyst for each trial. Helium, used

as the carrier gas, was delivered at flow rates of 40, 60, 80, and 100 mL/min. The furnace

temperature was adjusted between 400 °C and 520 °C. Before each cyclohexane injection, the

catalyst bed was held at the target temperature for one hour to achieve thermal stabilization.

Cyclohexane vapor was then introduced, and the reactor effluent was analyzed by a Hitachi gas

chromatograph fitted with a flame ionization detector (FID), which detects all hydrocarbons

39
except hydrogen and permanent gases. Each reaction was run for 60 seconds, and the resulting

product distribution was recorded in the online chromatogram

3.3.1 Experimental Procedure

The experimental procedure encompassed the following steps: setting up the equipment,

preparing the catalyst, pre-treating the catalyst, performing the cracking reaction on the pre-

treated catalyst, and analyzing the reaction products using Gas Chromatography.

[Link] Preliminary Preparation

Prior to setting up the equipment, the stainless steel tube with a 6 mm internal diameter was

flushed with purified air under pressure to remove any dust particles and contaminants present in

the pipe. The system was then tested for air-tightness by allowing helium to flow through it at a

pressure of 6.0 atm/Pa. This step was crucial to prevent the wastage of carrier gas and to

eliminate the risk of explosion.

[Link] Catalyst Pretreatment

The Zeolite Y catalyst was ground and sieved to a particle size range of 53-75 micrometers. This

size selection was based on the need to balance pressure drop and avoid diffusion limitations.

For each experimental run, 0.15g of the catalyst was loaded into the microcatalytic reactor. To

facilitate proper loading into the 6 mm diameter stainless steel reactor tube, a cellophane funnel

was used. Both ends of the reactor were then sealed with glass wool to prevent the catalyst from

being displaced during the experiment. The catalyst underwent pretreatment by drying it for 1

hour under a nitrogen flow of 40 mL/min at a temperature of 110°C inside an oven.

40
 Figure 3.4: Schematic diagram of typical GC set up (Francis and Annick, 2000)

The cracked cyclohexane sample was introduced into the gas chromatograph, where it was

vaporized and transported by a carrier gas through a column packed with the stationary phase.

Separation of components occurred through differential partitioning, governed by variations in

analyte solubility at the column temperature. The underlying principle of gas chromatography

(GC) relies on the interaction between the analyte and the stationary phase—compounds with

higher retention exhibit longer elution times due to stronger interactions with the stationary

medium.

The operation of the GC involved injecting the sample in its vapor phase directly into the

chromatographic column. Within the column, the extent to which each component remained in

the gas phase was influenced by its vapor pressure, the operating column temperature, and its

degree of affinity for the stationary phase. Molecular partitioning occurred between the gas

phase and the stationary phase due to differences in vapor pressures of the individual

components. This partitioning process persisted as the carrier gas propelled the molecules

41
through the column toward the detector. Owing to variations in vapor pressure, each compound

migrated at a unique rate, causing them to elute at different times. The detector response was

subsequently processed by the integrator, which displayed the results of the cracked products as

distinct peaks. Schematic representations of the gas chromatographic setup are presented in

Figures 3.4 and 3.5.

42
Figure 3.5: Gas Chromatograph system

43
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