SYNTHESIS AND CHARACTERIZATION OF MICROPOROUS ZEOLITE FROM NATURAL KAOLIN CLAY

OBTAINED FROM NSUKKA, ENUGU STATE AND ITS APPLICATION IN THE ADSORPTION OF DIVALENT
LEAD IONS FROM AQUEOUS SOLUTION

A RESEARCH SEMINAR

BY
DAVID, MOSES KOLADE
PG/MSC/15/79443

DEPARTMENT OF PURE AND INDUSTRIAL CHEMISTRY

UNIVERSITY OF NIGERIA, NSUKKA.

SUPERVISOR: PROF. U. C. OKORO

RESEARCH COORDINATOR: DR. L. N. OBASI
JANUARY, 2018
 OUTLINE
Introduction

Statement of Problem

Aim and Objectives

Literature Review

Methodology

Results and Discussion

Conclusion
 INTRODUCTION
Nanoporous Materials
• Consists of either an organic and/or inorganic framework
• Maintains a porous structure
• Large surface area in excess of 400m2/g

Classification
• Microporous: with pores of less than 2 nm in diameter
• Mesoporous: having pores between 2 and 50 nm
• Macroporous: with pores greater than 50 nm.
 INTRODUCTION

Applications
• Ion Exchange
• Separation
• Catalysis
• Sensor
• Biological Molecular Isolation
• Purifications
 INTRODUCTION
Zeolite
• Largest group of microporous materials
• Crystalline inorganic polymers
• Three-dimensional arrangement of SiO4 and AlO4 tetrahedra connected
through their oxygen atoms
• Large negatively-charged lattices with Brønsted and Lewis acid sites
• Synthetic microporous zeolites have pore diameters in the range of 0.3nm to
1.8nm

Figure 1. (a) TO4 tetrahedron; (b) TO4 tetrahedra sharing a common oxygen vertex
 STATEMENT OF PROBLEM
Heavy metals: A threat to human health and the environment and are present in
aqueous waste streams from many industries such as: Electroplating, Metal
Finishing, and Metallurgical Industries, Coal Combustion, Chemical
Manufacturing, Tanneries and Battery Manufacturing.

Clinical Effects: increased salivation, severe stomach irritations leading to

vomiting and diarrhea, abdominal pain, choking, high blood pressure, iron-poor
blood, liver disease, pancreas and nerve or brain damage etc., as a result, the
removal of heavy metal ions from water has become an important subject today.
 STATEMENT OF PROBLEM

Various methods for the removal of heavy metals have been carried out, such as
chemical precipitation, solvent extraction, ion exchange, reverse osmosis or
adsorption, and so on (Fu & Wang 2011; Mohan & Gandhinathi 2009; Yaday et
al., 2013).

However, most of these methods have limitations, which include high cost,
unavailability, and generation of large volumes of secondary waste and poor
removal efficiency (Esalah et al., 2000; Gupta et al., 2001; Kang et al., 2008).
 STATEMENT OF PROBLEM
Considering from the economy and efficiency point of view, adsorption is
regarded as the most promising and extensively used method (Manohar et al.,
2006).

Therefore, searching for alternative low-cost adsorbents for the removal of

heavy metal ions is highly desired.
 AIM AND OBJECTIVES OF THE STUDY
The aim of this study is to synthesize a cost-effective zeolite adsorbent to
remove divalent lead ions from aqueous solution.

The study will be guided by the following objectives:

• To synthesize microporous zeolite from natural Kaolin Clay via
hydrothermal process.
• To characterize the synthesized zeolite and raw kaolin using analytical
techniques such as XRF, BET, XRD, SEM, FTIR and AAS.
• To adsorb lead metal ions from aqueous solution using the synthesized
zeolite.
 LITERATURE REVIEW
HYDROTHERMAL APPROACH TO ZEOLITE SYNTHESIS

Zeolites were first discovered to occur naturally

Their unique properties were becoming popular and the naturally existing
zeolites could no longer meet up with industrial needs

Scientists began to look for ways to synthesize artificial ones

The only very successful approach adopted over the years for zeolite synthesis
is the Hydrothermal Approach
 LITERATURE REVIEW
HYDROTHERMAL APPROACH TO ZEOLITE SYNTHESIS
Hydrothermal synthesis refers to the synthetic reactions conducted at appropriate temperature
(100~1000 0C) and pressure (1~100 MPa) in aqueous or organic solvents within a specially
sealed container or high-pressure autoclave (Xu et al., 2007).

Figure 2a. Hydrothermal synthesis of zeolites Figure 2b. Autoclaves

 LITERATURE REVIEW
HYDROTHERMAL APPROACH TO ZEOLITE SYNTHESIS

Conventionally, zeolites are synthesized from aqueous basic aluminosilicate

precursor gels under hydrothermal conditions.

These reactions are usually expensive to carry out, hence there is need utilize
other inexpensive and cost effective sources of silica and alumina.

In view of this, researchers in different parts of the world try to employ other
materials as alternative and inexpensive sources of silica and alumina in zeolite
synthesis.
These alternative sources include; kaolin clay, coal fly ash, rice husk ash and
oil shale ash
 LITERATURE REVIEW
Kaolin Clay (Ulo)
Clay mineral with chemical composition Al2Si2O5(OH)4.
It is a layered silicate mineral with one tetrahedral sheet of silica linked through
oxygen atoms to one tetrahedral sheet of alumina octahedron.

Figure 3a. Raw kaolin clay sample Figure 3b. Structural formula of kaolin
 Zeolites from Natural Kaolin Clay
Mostafa et al,. (2011) reported that Zeolite-A was synthesized from Egyptian kaolin through
metakaolinization and zeolitization.
 Effect of various controlling parameters on Zeolite-A preparation was investigated. These
include temperature and time of metakaolinization, solid to liquid (S/L) ratio, NaOH
concentrations and processing time of zeolitization.
 Zeolite-A were characterized by X-Ray Diffraction (XRD) and Scanning Electron
Microscope (SEM).
They concluded that the lab-scale formation of zeolite-A from the Egyptian kaolin was
successful under the following conditions: 800oC/12h for the kaolin calcination, 100oC/3h for
the reaction time and temperature, 0.5- 1.5: 5 for the solid/liquid ratio and: 3.0 M NaOH for
the alkali concentration.
 Coal Fly Ash (CFA)

One of the coal combustion residuals (CCRs)

Fine powder composed mostly of silica and alumina

Figure 4. Coal fly ash deposits

 Zeolites from Coal fly Ash (CFA)
In Guyo et al., (2013), disposed coal fly ash samples from Zimbabwe were used in synthesis
of zeolites.

The method of direct hydrothermal treatment with sodium hydroxide at different

concentrations (2, 2.5, 3.5 and 4.5 moldm-3) at a constant temperature of 100°C and
activation time of 24 h was applied.

Characterisation of coal fly ash and confirmation of occurrence of the zeolite material was
done using XRF, XRD, FTIR, and BET techniques.

The zeolite materials formed were a mixture of zeolite Na-X, zeolite Na-A zeolite NaP1 and
zeolite hydroxysodalite. The variety and yield of zeolites formed depend on the concentration
of sodium hydroxide used.
 Rice Husk Ash (RHA)
Residual of rice husk combustion

Characterized with high silica content

Figure 5. Rice husk ash deposits

 Zeolites from Rice Husk Ash (RHA)

Bohra et al., 2013 reported the production of zeolite T by direct dissolution of

rice husk ash in aqua-based raw materials following an inexpensive process.

They found that the direct extraction of silicate from rice husk ash was in favor
of the crystallization of zeolite T particles at 100oC for 24 h.

They also observed that crystallization increased with increase in reaction time.

They concluded that the locally available agro-waste material, RHA which is
environmentally hazardous can be converted to advanced zeolite and zeolite-
type materials in an economic and environmentally friendly process.
 Oil Shale Ash (OSA)

A by-product of oil shale processing

It is composed majorly of silica and alumina

Figure 6a. Burning oil shale Figure 6b. Spent oil shale
 Zeolites from Oil Shale Ash (OSA)

Shawabkeh et al., 2004 reported the conversion of a by-product fly ash from oil
shale into zeolite by alkali hydrothermal reaction using sodium hydroxide.

The zeolitization process of oil shale ash was optimally synthesized at the
experimental conditions of: 8 M sodium hydroxide solution, 160oC and 1–24 h
reaction times.

Powder patterns of X-ray diffraction analysis did show that zeolite of type Na-PI
was successfully synthesized at 29.5, 32.2 and 34.48o
 LEAD TOXICITY IN WATER
Lead is the most popular of all the heavy elements, occupying up to 13 mg/kg of Earth’s crust.

Lead is applied in the manufacture of lead acid batteries, solder, alloys, cable sheathing, pigments,
rust inhibitors, ammunition, glazes and plastic stabilizers.

From a drinking-water viewpoint, the almost common use of lead compounds in plumbing fittings
and as solder in water distribution systems is important (WHO, 2011).

signs such as irritability, weight loss, vomiting, constipation, or stomach pain could occur from lead
exposure. Young children and pregnant women are at the utmost risk, even from short term exposure.

Impeded intellectual growth and neurobehavioral insufficiencies are related with blood levels less
than 10 micrograms of lead per deciliter of blood in children (ATSDR, 2007).

Thus, it is determined that there is no safe blood lead level in children (CDCP, 2017).
 ADSORPTION OF LEAD IONS USING ZEOLITES
Jha et al., 2008 reported that when Pb2+ uptake experiments were carried out at the
Pb2+ content range from 100 to 2,000 mg/L at 25C for 24 h using composites of
activated carbon/zeolite prepared from coal fly ash as adsorbent, its uptake capacity
for Pb can reach to be 228 mg/g.

The intake capacity of natural zeolite from Croatia for the metal Pb is about 78.7
mg/g at the conditions of sorption temperature of 70oC, pH 4.5, and sorption time of
24 h, obviously higher than 10 mg/g intake capacity of Turkey zeolite (Bekta &
Kara, 2004). After Croatia natural zeolite was treated with 2 M NaCl solution at 70oC
for 24 h, the Pb sorption quantity was increased to 91.2 mg/g at the same experiment
conditions
 METHODOLOGY
Reagents Instruments
• Sodium hydroxide pellets (99% NaOH) • Nova 4200e Surface Area and Pore Analyzer
• Hydrochloric acid • Empyrean by Panalytical
• Lead nitrate • Thermo Scientific™ Q250 Scanning Electron Microscope
• Kaolin clay (SiO2, Al2O3, TiO2 and oxides of • Agilent Cary 630 FTIR spectrometer
other compounds) • 8000 X-ray Fluorescence Analyzer
• Deionized water
• Shimadzu’s AA-7000 Atomic Adsorption
Spectrophotometer
• Searchtech SXL muffle furnace
• 100ml PTFE Vessel/Autoclave
• Ohaus AR3130 top loading analytical weighing balance
• Jenway 3510 electronic pH meter
• Gallenkamp oven BS model OV-160
• Searchtech 78HW-1 constant temperature magnetic stirrer
 METHODOLOGY
Preparation of Standard Solutions
• Sodium Hydroxide Solution (0.5mol = 20g/1L, 1.5M = 60g/L and 2.5M =
100g/L)
• Lead Solution (225mg/L)
Kaolin Sample Collection
Zeolite Synthesis
The synthesis was carried out by modifying the work of Ismail et al., (2013)
• Metakaolinization (800oC/2h)
• Zeolitization
 METHODOLOGY

Synthesis Flow Chart

Raw Thermal Reaction Filtration/Drying

Kaolin Activation Mixture Crystallization
 METHODOLOGY
Characterization
• XRF, BET, FTIR, XRD, SEM, AAS

Adsorption Experiments
• 0.5g zeolite/50ml lead solution (225mg/l)
• Reaction time = 20mins
• Reaction temperature = 50oC
• The residual metal ion was determined by AAS
 METHODOLOGY
• The removal efficiency (R) and adsorption capacity (q) were calculated using
the following equations (He et al., 2015):
R = C0 – C1/C0 (1)

q = (C0 – C1)V/C0 (2)

where
C0 is the initial concentration of heavy metal ions (mg/L)
C1 is the residual concentration of metal ions (mg/L)
V is the volume of solution (L)
m is the mass of the adsorbent (g)
 Results and Discussion
Table 1. Chemical Composition of Nsukka Kaolin
Element Concentration (Wt%)
Na2O 0.000
MgO 3.806
Al2O3 19.45
SiO2 60.341
P2 O 5 0.013
SO3 0.306
Cl 0.020
K2 O 0.807
CaO 0.883
TiO2 1.852
Cr2O3 0.042
Mn2O3 0.224
Fe2O3 12.198
ZnO 0.024
SrO 0.032
 Results and Discussion
Table 2. BET Surface Area and Pore Parameters of Samples

Samples Surface area (m2/g) Pore volume (cc/g) Pore diameter (nm)

A 19.170 0.0065 1.360

B 247.889 0.0884 1.080

C 208.745 0.0889 1.320

D 221.608 0.0642 1.160

Sample A = Raw Kaolin

Gas used = Nitrogen
 Results and Discussion
Figure 7. Plot of samples against BET surface area (m2/g)
300

247.889
250
221.608
208.745
SURFACE AREA

200

150

100

50
19.17

0
A B C D
SAMPLES
 Results and Discussion
Figure 8. Plot of samples against pore volume (cc/g)
0.08

0.06899
0.07 0.06684
0.0642

0.06
PORE VOLUME

0.05

0.04

0.03

0.02

0.01 0.006504

0
A B C D
SAMPLES
 Results and Discussion
Figure 9. Plot of samples against pore diameter (nm)

1.6

1.4 1.36
1.32
PORE DIAMETER

1.2 1.16
1.08

0.8

0.6

0.4

0.2

0
A B C D
SAMPLES
 Results and Discussion
Figure 10. Plot of samples against lead adsorption capacity (mg/g)
25

19.7
ADSORPTION CAPACITY

20 18.65 19.13

15

10
7.3

0
A B C D

SAMPLES
 Results and Discussion
Figure 11. Lead removal efficiencies (%)
100

90 88
83 85
REMOVAL EFFICIENCY

80

70

60

50

40
33
30

20

10

0
A B C D
SAMPLES
 Results and Discussion
Figure 12. XRD pattern of sample C
3500

3000

2500
Intensity (Counts)

2000

1500

1000

500

0
0 10 20 30 40 50 60 70 80

2 Theta (Degrees)

Reflection peaks at 2θ = 7-9° and 2θ = 22-25° indicates the typical structure of

ZSM-5 (Zeolite Socony Mobil)
 Results and Discussion
Figure 13. SEM micrographs of samples A and C

SEM micrographs (13a&b) shows that kaolin have mainly amorphous structure
SEM micrographs (13c&d) shows a spherical crystalline morphology of ZSM-5
 Results and Discussion
Table 3. Chemical composition of sample C
Element Concentration (Wt%)
Na2O 6.727
MgO 4.228
Al2O3 19.493
SiO2 52.678
P2 O 5 0.000
SO3 0.215
Cl 0.035
K2O 0.565
CaO 1.056
TiO2 1.945
Cr2O3 0.039
Mn2O3 0.214
Fe2O3 12.750
ZnO 0.025
SrO 0.029
 Results and Discussion
Figure 14. FT-IR Spectra of sample C

The broad band at 3291 cm-1 and the sharp peak at 1640 cm-1 are attributed to
the structural hydroxyl groups and bending mode of physically adsorbed water
respectively.
Band around 1148 cm-1 is represents T-O (T=Si or Al) symmetric stretching.
Bands associated with the asymmetric and symmetric stretching vibrations of T-
O-T bridges are at 1077 cm-1 and 760 cm-1.
 Conclusion
In this present study, raw kaolin obtained from Nsukka was used in the
synthesis of zeolites via hydrothermal reaction with NaOH as an alternative
source of silica and alumina.

BET surface area and pore volumes of all the prepared samples were found to
have increased significantly when compared to the parent kaolin, there was a
decrease in pore diameter of the prepared samples relative to the starting raw
kaolin.

XRF showed that the raw kaolin contains substantial amount of silica and
alumina for zeolitization.
 Conclusion
Performance assessment was carried out on all the prepared samples, lead
removal efficiency increased up to 88%. When compared to the 33% removal
efficiency recorded from the performance of the raw kaolin, the synthesized
samples performed better which is in accordance to the findings of several
authors.
XRD peaks, SEM micrographs and FT-IR spectroscopy confirmed the
formation of ZSM-5 in the sample with the highest lead removal efficiency.
The experimental result regarding the adsorption characteristic of synthetic
ZSM-5 prepared from Nsukka kaolin for the removal of divalent lead ions from
aqueous solution showed that Nsukka kaolin exhibits a great potential as a raw
material for the production of low cost adsorbents.
THANK YOU FOR LISTENING